Basic triphendioxazine dyestuffs

ABSTRACT

Basic triphendioxazine dyestuffs of the formula ##STR1## wherein Q denotes the radical ##STR2##  or hydrogen, R 1  and R 2 , independently of each other, denote hydrogen, halogen, alkyl, aryl, alkoxy, aryloxy, CN, CONH 2 , CONH--alkyl, CON(alkyl) 2 , CONH--aryl, COO--alkyl, NH--CO--alkyl or NH--CO--aryl and 
     R 3  and R 4 , independently of each other, each denote hydrogen or alkyl, or 
     R 3  and R 4  are joined together into a ring, 
     A denotes a divalent hydrocarbon radical which is optionally interrupted by oxygen or sulphur, 
     R 5  denotes a radical of a polyamine which can be protonated or quaternized, 
     R 6  is defined the same way as R 5  or denotes NH 2 , NH--alkyl, N(alkyl) 2 , wherein the two alkyl radicals can be joined together to form a ring, NH--cyclohexyl, NH--aryl, N(alkyl)--aryl, NH--aralkyl, N(alkyl)-aralkyl, OH, alkoxy, aryloxy, alkyl or aryl, 
     m denotes 0 or 1 and 
     n denotes 0-2 with the proviso that n is less than the total number of protonatable or quaternizable nitrogen atoms in R 5  and R 6 , 
     and wherein said cyclic and acyclic substituents can in turn be substituted by nonionic or cationic radicals customary in dyestuff chemistry, are used in particular for dyeing paper.

The present invention relates to basic triphendioxazine dyestuffs of theformula ##STR3## wherein Q denotes the radical ##STR4## or hydrogen, R₁and R₂, independently of each other, denote hydrogen, halogen, alkyl,aryl, alkoxy, aryloxy, CH, CONH₂, CONH--alkyl, CON(alkyl)₂, CONH--aryl,COO--alkyl, NH--CO--alkyl or NH--CO--aryl and

R₃ and R₄, independently of each other, each denote hydrogen or alkyl,or

R₃ and R₄ are joined together into a ring,

A denotes a divalent hydrocarbon radical which is optionally interruptedby oxygen or sulphur,

R₅ denotes a radical of a polyamine which can be protonated orquaternised,

R₆ is defined the same way as R₅ or denotes NH₂, NH--alkyl, N(alkyl)₂,wherein the two alkyl radicals can be joined together to form a ring,NH--cyclohexyl, NH--aryl, N(alkyl)--aryl, NH--aralkyl,N(alkyl)--aralkyl, OH, alkoxy, aryloxy, alkyl or aryl,

m denotes 0 or 1 and

n denotes 0-2,

and wherein said cyclic and acyclic substituents can in turn besubstituted by nonionic, cationic or anionic radicals customary indyestuff chemistry, and the rings a can be substituted by nonionicradicals customary in dyestuff chemistry, with the proviso that thetotal number of anionic groups is less than the total number ofprotonatable or quaternisable nitrogen atoms in R₅ and R₆, to theirpreparation, to their aqueous solutions and to their use for dyeingcationically dyeable substrates, in particular paper.

For the purposes of the present invention, an optionally protonated orquaternised polyamine radical R₅ is preferably a diamine, triamine ortetramine radical and in particular a radical of the formulae ##STR5##wherein R₇ -R₁₀ each denote hydrogen or alkyl and

R₁₁ denotes hydrogen, alkyl or aralkyl, or

R₇ and R₈ or R₇ and R₁₀ or R₈ and R₁₀ or R₈ and R₉ or R₈, R₉ and R₁₁ arejoined together to form a ring,

B represents optionally branched C₂ -C₆ -alkylene, cyclohexylene,phenylene or a radical of the formulae ##STR6## X.sup.(-) represents ananion, and wherein the said cyclic and acyclic radicals can in turn besubstituted by nonionic or cationic radicals customary in dyestuffchemistry.

In the formula (I), R₁ and R₂ each preferably represent halogen and inparticular chlorine.

In the formulae (I)-(V), an alkyl radical is to be understood asmeaning, above all, a radical having 1-4 carbon atoms.

Aryl and aralkyl preferably represent phenyl and benzyl or phenylethylrespectively.

Examples of nonionic substituents which come into consideration arehalogen, such as fluorine, chlorine, or bromine, hydroxyl, C₁ -C₄-alkoxy, cyano, C₁ -C₄ -alkyl and amino.

The cationic substituent in question is especially the ammonium groupand the anionic substituent the sulphato group.

However, nonionic and cationic substituents are preferred. The radical Arepresents, for example, optionally branched alkylene having 2-6 C atomswhich can be interrupted by O or S or be substituted by OH, or theradicals: ##STR7## which can be substituted by C₁ -C₄ alkyl.

The radicals

R₃ and R₄, together with --N--A--N--,

R₇ and R₈, together with --N--B--N--,

R₇ and R₁₀, together with --N--B--N-- or

R₈ and R₁₀, together with --N--B--N--,

can form a 5- or 6-membered ring, for example a piperazine orimidazolidine ring.

The radicals R₈ and R₉ on the one hand and the radicals R₈, R₉ and R₁₁on the other, together with N, can form a 5- or 6-membered ring, forexample a piperidine, morpholine, piperazine or pyrrolidine ring and apyridine ring respectively.

Said heterocyclic structures can carry further substituents, such as C₁-C₄ -alkyl radicals, or a fused-on ring, for example a benzene ring.

Particular examples of anions X.sup.(-) are: chloride, bromide, iodide,sulphate, hydrogensulphate, methylsulphate, ethylsulphate, sulphamate,perchlorate, phosphate, hydroxide, formate, acetate, propionate,oxalate, malonate, succinate, maleinate, chloroacetate,trichloroacetate, methoxyacetate, ethoxyacetate, lactate, citrate,benzoate, methanesulphonate, ethanesulphonate, benzenesulphonate,p-toluenesulphonate and carbonate.

Examples of R₁ and R₂ are: hydrogen, chlorine, bromine, C₁ -C₄ -alkyl,phenyl, chlorophenyl, methylphenyl, C₁ -C₄ -alkoxy, acetylamino,propionylamino, butyrylamino, benzoylamino, methylbenzoylamino,chlorobenzoylamino, phenoxy, chlorophenoxy, methylphenoxy,anilinocarbonyl, toluidinocarbonyl, chloroanilinocarbonyl,methoxycarbonyl and ethoxycarbonyl.

Radicals R₃ and R₄, in addition to hydrogen, are for example C₁ -C₄-alkyl, β-hydroxyethyl or β-sulphatoethyl.

Examples of alkylene radicals A are ethylene, 1,2-propylene,1,3-propylene, 1,4-butylene, 1,3-butylene, 2,3-butylene,2-methyl-1,3-propylene, 2-hydroxy-1,3-propylene, 1,5-pentylene,1,6-hexylene, 2,5-hexylene, --CH₂ --CH₂ --O--CH₂ --CH₂ --, --CH₂ --CH₂--S--CH₂ --CH₂ --, 2,2-dimethylpropylene, 2-methyl-2,4-pentylene, 1,2-,1,3- and 1,4-cyclohexylene, 4-methyl-1,3-cyclohexylene. ##STR8##

Examples of R₅ are: 2-dimethylamino-1-ethylamino,2-diethylamino-1-ethylamino, 2-(β-hydroxyethylamino)-1-ethylamino,2-bis-(β-hydroxyethyl)-amino-1-ethylamino,N-(2-dimethylamino-1-ethyl)-N-methylamino, 2-methylamino-1-ethylamino,N-(2-ethylamino-1-ethyl)-N-ethylamino, 3-dimethylamino-1-propylamino,3-diethylamino-1-propylamino, 3-methylamino-1-propylamino,3-ethylamino-1-propylamino, 3-(β-hydroxyethylamino)-1-propylamino,3-bis-(β-hydroxyethyl)-amino-1-propylamino,3-(N-methyl-N-β-hydroxyethyl)-amino-1-propylamino,5-dimethylamino-2-pentylamino, 5-diethylamino-2-pentylamino,2-amino-1-ethylamino, 3-amino-1-propylamino, 4-amino-1-butylamino,5-amino-1-pentylamino, 6-amino-1-hexylamino,3-amino-2-hydroxy-1-propylamino, 2-(N-morpholino)-1-ethylamino,2-(N-piperazinyl)-1-ethylamino or N-(N'-2-aminoethyl)-piperazino,2-[N-(N'-methyl)piperazinyl]-1-ethylamino,2-(N-piperidinyl)-1-ethylamino, 3-(N-piperazinyl)-1-propylamino, orN-(N'-3-aminopropyl)-piperazino,3-[N-(N'-methyl)-piperazinyl]-1-propylamino,3-(N-morpholino)-1-propylamino, piperazinyl, N-methyl-N'-piperazinyl,N-ethyl-N'-piperazinyl, 3-(N-piperidinyl)-1-ethylamino,3-(N-pyrrolidinyl)-1-propylamino, 2-(N-pyrrolidinyl)-1-ethylamino,N-(β-hydroxyethyl)-N'-piperazinyl, 4-amino-1-cyclohexylamino,3-amino-1-cyclohexylamino, 4-, 3- or 2-dimethylaminophenylamino,4-(β-diethylaminoethoxy)-phenylamino,4-N-(3'-dimethylamino-1'-propylamino)-phenylamino,4-N-(2'-dimethylamino-1'-ethylamino)phenylamino,3-(N-methyl-N-γ-aminopropyl)-1-propylamino, and also the radicals ofdiethylenetriamine, triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine andthe radicals ##STR9## as well as the ammonium salts of these amineswhich carry as the fourth radical on the nitrogen for example a C₁ -C₄-alkyl group, hydroxyethyl, hydroxypropyl, dihydroxypropyl,methoxycarbonylethyl or benzyl.

Examples of radicals R₆, in addition to R₅, are NH₂, OH, C₁ -C₄-alkylamino, di-(C₁ -C₄ -alkyl)-amino, β-hydroxyethylamino,bis-(β-hydroxyethylamino), morpholino, piperidino, cyclohexylamino,benzylamino, N-methyl-N-benzylamino, N-methyl-N-(β-hydroxyethyl)-amino,phenylamino, 2-, 3- or 4-methylphenylamino, 2-, 3- or4-chlorophenylamino, 2-, 3- or 4-methoxyphenylamino, 2-, 3- or4-acetylaminophenylamino, 2-, 3- or 4-benzoylaminophenylamino and 2-, 3-or 4-ureidophenylamino.

Preferred dyestuffs of the formula (I) have the formula ##STR10##wherein R'₁ and R'₂ each denote hydrogen or halogen,

R'₃ and R'₄ each denote hydrogen or C₁ -C₄ -alkyl which can besubstituted by OH or sulphato,

A' denotes optionally branched C₂ -C₆ -alkylene which can be interruptedby O or S or be substituted by OH or the radicals ##STR11## which can besubstituted by C₁ -C₄ -alkyl, or ##STR12## represents optionally C₁ -C₄-alkyl-substitutable piperazine, R'₅ denotes a radical of the formula##STR13## R'₇ -R'₁₁ each denote hydrogen or C₁ -C₄ -alkyl which isoptionally substituted by hydroxyl, C₁ -C₄ -alkoxy, halogen, cyano, C₁-C₄ -alkoxycarbonyl or C₁ -C₄ -alkylcarbonyl and

R'₁₁ also denotes optionally C₁ -C₄ -alkyl-, hydroxyl-, C₁ -C₄ -alkoxy-or halogen-substituted benzyl or phenylethyl and

B denotes C₂ -C₆ -alkylene, cyclohexylene, phenylene or an optionally C₁-C₄ -alkyl-substituted radical of the formulae ##STR14## an optionallyC₁ -C₄ -alkyl-substituted piperazine or imidazolidine ring, or

R'₈ --N--R'₉ signifies an optionally C₁ -C₄ -alkyl-substitutedpiperidine, morpholine, piperazine or pyrrolidine ring or ##STR15##signifies an optionally C₁ -C₄ -alkyl-substituted pyridinium radical,

X.sup.(-) signifies an anion,

R'₆ is defined in the same way as R'₅ or represents ##STR16## OR'₈ orOR₁₂ where R₁₂ =optionally C₁ -C₄ -alkyl-, hydroxyl-, C₁ -C₄ -alkoxy- orhalogen-substituted phenyl, benzyl, phenylethyl or cyclohexyl and mdenotes 0 or 1.

In preferred dyestuffs of the formula (VI), R'₁ and R'₂ each representchlorine, R'₃ and R'₄ each represent hydrogen or C₁ -C₄ -alkyl, and R'₆represents R'₅.

Particularly noteworthy dyestuffs have the formula ##STR17## wherein R'₅is as defined above and

q represents 2, 3 or 4,

and the formula ##STR18##

Of these, attention should in turn be drawn to those of the formula(VII) or (VIII) wherein

q represents 2 or 3,

R'₅ represents --NH--(CH₂)₃ --N(R'₁₂)₂ ##STR19## R'₁₂ representshydrogen, methyl or ethyl and R₁₃ represents OH or N(R'₁₂)₂, and inparticular to their salts obtained by reaction with quaternising agentsof the formula

    R'.sub.11 --X                                              (IX)

wherein

R'₁₁ represents hydrogen, methyl or ethyl and

X represents a radical detachable in the form of an anion X.sup.(-).

Said dyestuffs (I) are prepared by condensing dyestuff bases of theformula ##STR20## wherein R₁, R₂, R₃, R₄, A, m and n are as definedabove, with trihalogenotriazines of the formula ##STR21## wherein Y=F,Cl or Br,

to give compounds of the formula ##STR22## wherein R₁, R₂, R₃, R₄, A, Y,m and n are as defined above and

Q₁ represents hydrogen or the radical ##STR23## and by reacting thesecompounds further in any order--through elimination of hydrogenhalide--with compounds of the formulae

    R.sub.5 --H                                                (XIII)

or with R₅ --H and

    R.sub.6 --H                                                (XIV)

wherein

R₅ and R₆ are as defined above.

In an alternative method for compounds of the formula (I), dyestuffbases of the formula (X) are condensed with substituteddihalogenotriazines of the formula ##STR24## wherein R₅, R₆ and Y are asdefined above, to give respectively compounds of the formulae ##STR25##wherein R₁, R₂, R₃, R₄, R₅, R₆, A, Y, Q₁, m and n are as defined above,

and these compounds are condensed with compounds of the formulae (XIII)and (XIV) respectively.

Triphendioxazine compounds of the formula (X) can be prepared, forexample, by condensing substituted benzoquinones with optionallyappropriately substituted 1,4-phenylenediamines or the sulphonic acidsthereof and subsequently cyclising the condensation products obtained asdescribed in German application Nos. DE-A-2,122,262, 2,124,080,2,503,611 and 2,823,828. It is also possible to react nitroaminophenolswith substituted benzoquinones, as is described in German PatentSpecification No. 620,346, and to reduce the nitro groups in theresulting nitrotriphendioxazines to amino groups.

Said dyestuff bases (X) are condensed with said trihalogenotriazines(XI) at temperatures of 0°-40° C., preferably 0°-20° C., and pH 3-10 inaqueous or aqueous-organic media in the presence of alkaline condensingagents, such as aqueous alkali metal hydrogencarbonate, alkali metalcarbonate, alkali metal hydroxide or alkali metal phosphate solution; orthe condensation is carried out at temperatures of 0°-20° C. in aproticorganic solvents such as toluene, halogenobenzenes, nitrobenzene,dimethylformamide, N-methylpyrrolidone, tetramethylene sulphone,dimethyl sulphoxide, acetone or methylethylketone in the presence ofaprotic organic bases, such as trialkylamines, N,N-dialkylanilines,pyridine or alkylpyridines.

The second halogen atom in compounds of the formula (XII) is generallyreplaced, depending on the nature of Y, at temperatures between 0°-60°C. and at pH 4-11, preferably pH 5-10. These conditions also apply tothe condensation of dihalogenotriazine components (XV) and (XVI) withdyestuff bases (X).

The replacement of the third halogen atom, in order to arrive atcompounds of the formula (I), can be obtained at temperatures between30° and 100° which can be allowed for through appropriate temperaturecontrol if products of the formula (I) are to be prepared from compounds(XII).

The replacement of the third halogen atom in compounds (XII) or of thesecond and third halogen atoms in compounds (XVII) and (XVIII) can ofcourse also be carried out in excess amounts of components (XIII) and(XIV) respectively in the presence or absence of water or organicsolvents.

The basic dyestuffs obtained by the methods which have been demonstratedare made ready for application by dissolving them in the dilute acidseither directly or, if necessary, after prior isolation, or they arequaternised with quaternising agents (IX) in water, aqueous-organic ororganic solvents and optionally isolated for the purpose of subsequentlypreparing pure aqueous solutions.

The new basic dyestuffs can be used in protonated or quaternised form,when they are readily water-soluble, for dyeing, from aqueous solutions,a very wide variety of different materials, such as cellulose materials,polyacrylonitrile, acid-modified nylon and polyester, wool and leather.

The dyestuffs according to the invention are highly suitable above allfor dyeing a very wide variety of different types of paper in brightblue to violet shades.

The degrees of exhaustion obtained on dyeing are high, as evidenced bythe low concentration of dyestuff in the waste water. The dyeings havegood to very good light and wet fastness properties. They are highlyresistant to the action of water, alcohols, soaps or aqueous organicacids.

EXAMPLE 1

12.0 g of a triphendioxazine component of the formula ##STR26## aredissolved at pH 11.5 in 180 ml of water. 120 ml of acetone are added,and the solution is brought to pH 10.5.

A solution of 8.4 g of cyanuric chloride in 80 ml of acetone is added to80 g of ice. To the resulting cyanuric chloride suspension is added,dropwise, at 0° to 6° C. the solution of the triphendioxazine componentwhile pH 8.5 is maintained by controlling the rate of dropwise additionand adding 1N sodium hydroxide solution. Stirring is continued for abouta further 2 hours, until the condensation has ended. The condensationmixture is raised to room temperature, the condensation product issalted out with sodium chloride, the precipitate is filtered off withsuction, and the filter cake is washed with 10% strength sodium chloridesolution.

The product obtained is introducted into a solution of 29.0 g of3-dimethylamino-1-aminopropane in 180 ml of water. The temperature israised to 50° for 1 hour and then to 75° to 80° for a further 4 hours.The resulting solution is cooled down. The resulting product isprecipitated by adding 25% strength sodium chloride solution and isfiltered off with suction, and the filter cake is washed with 20%strength sodium chloride solution and then with 15% strength sodiumchloride solution and is dried.

The result is a dyestuff of the formula (VII) in which q=2 and R'₅=NH--CH₂ --CH₂ --CH₂ --N(₃)₂

max=637 nm in 5% strength acetic acid.

To dye paper, the product is dissolved in 10% strength acetic acid. Thepapers dyed in bright blue shades have very good light fastness andexcellent wet fastness properties. C.I. indicator number 14.

EXAMPLE 2

10.0 g of the triphendioxazine compound of the formula ##STR27## aredissolved in 400 ml of water by means of 34 ml of 1N sodium hydroxidesolution. This solution is added dropwise at 0° to 5° to a suspension of10.5 g of cyanuric chloride in 140 ml of water and 1.0 g of anemulsifier based on lauryl alcohol and ethylene oxide at such a rate asto establish pH 8.5-8.8. After all the solution has been dripped, insaid pH is maintained further by the dropwise addition of 1N sodiumhydroxide solution until the condensation is complete, which takesseveral hours. 20.0 g of 2-aminoethylpiperazine are then added to thefinely dispersed suspension of the condensation product, and the mixtureis initially heated at 60° for 2 hours and then at 95° for 5 hours. Themixture is cooled down, the partially precipitated product is salted outcompletely with sodium chloride and is filtered off with suction, andthe filter cake is washed with concentrated sodium chloride solution andthen with 10% strength sodium chloride solution.

The compound obtained has the formula (VII) where q=2 and R'₅ =##STR28##

λ_(max) 641 nm in 5% strength acetic acid.

The dyestuff is made ready for dyeing paper by dissolving it in diluteacetic acid. It produces on paper blue dyes having excellent fastnessproperties. High degrees of exhaustion are obtained on dyeing sized andunsized paper. C.I. indicator number 14.

EXAMPLE 3

12.0 g of the triphendioxazine component of Example 1 are reacted with8.4 g of cyanuric chloride, and the bis-(dichlorotriazinyl) condensationproduct is then isolated as described there. The filter cake obtained isintroduced into a mixture of 23.0 g of 2-hydroxyethylpiperazine and 250ml of water. The mixture is heated initially at 50° for 1 hour and thenat 95° to 100° for 3 hours. After the mixture has cooled down, thereaction product, which has partly crystallised out in the form ofneedles, is salted out as far as possible by the dropwise addition of25% strength sodium chloride solution, is filtered off with suction, iswashed with dilute sodium chloride solution and is dried.

The product obtained has the formula (VII) where q=2 and R'₅ = ##STR29##

λ_(max) =635 nm in 5% strength acetic acid.

For the dyeing of paper, the product is dissolved in dilute acetic acid.This solution can be used to dye paper in brilliant neutral blue shades.The dyeings have excellent light fastness properties and good wetfastness properties. The slight discolouration of the waste water afterthe dyeing demonstrates the high affinity of the dyestuff for cellulosematerial. C.I. indicator number 15.

EXAMPLE 4

Example 2 is repeated, except that the triphendioxazine component usedthere is replaced by 10.4 g of the following compound ##STR30##affording a product of the formula (III) where q=3 R'₅ = ##STR31##

λ_(max) =639 nm in 5% strength acetic acid

which is similarly used in a weakly acid solution for dyeing paper inbright blue shades. This product likewise produces excellent wetfastness properties on the dyed paper and high degrees of exhaustion.C.I. indicator number 14.

The triphendioxazine components listed in column 2 of Table I can becondensed analogously to Examples 1 to 3 with 2 moles of cyanuricchloride and the resulting intermediates can be reacted with 4 moles ofthe amine of column 3, the products being in every case basic bluedyestuffs of the formula (I) which are soluble in weak acids. C.I.indicator number 14.

    TABLE I      Example No. Triphendioxazine component Amine          5      ##STR32##      ##STR33##      6     ##STR34##      NH.sub.2(CH.sub.2).sub. 3N(CH.sub.2CH.sub.2 OH).sub.2      7     ##STR35##      ##STR36##      8     ##STR37##      ##STR38##      9     ##STR39##      H.sub.2 N(CH.sub.2).sub.3N(C.sub.2 H.sub.5).sub.2      10     ##STR40##      ##STR41##      11     ##STR42##      NH.sub.2(CH.sub.2).sub.2N(C.sub.2 H.sub.5).sub.2      12     ##STR43##      NH.sub.2(CH.sub.2).sub.2N(CH.sub.2CH.sub.2 OH).sub.2      13     ##STR44##      NH.sub.2(CH.sub.2CH.sub.2NH).sub.2CH.sub.2CH.sub.2NH.sub.2      14     ##STR45##      ##STR46##      15     ##STR47##      ##STR48##      16     ##STR49##      ##STR50##      17     ##STR51##      ##STR52##      18     ##STR53##      NH.sub.2(CH.sub.2).sub.3N(CH.sub.3).sub.2      19     ##STR54##      NH.sub.2(CH.sub.2).sub.3N(C.sub.2 H.sub.5).sub.2      20     ##STR55##      ##STR56##      21     ##STR57##      ##STR58##      22     ##STR59##      NH.sub.2(CH.sub.2).sub.2N(CH.sub.3).sub.2      23     ##STR60##      ##STR61##      24     ##STR62##      ##STR63##      25     ##STR64##      ##STR65##      26     ##STR66##      H.sub.2 N(CH.sub.2).sub.3N(CH.sub.3).sub.2      27     ##STR67##      H.sub.2 N(CH.sub.2).sub.3N(C.sub.2 H.sub.5).sub.2      28     ##STR68##      ##STR69##      29     ##STR70##      H.sub.2 N(CH.sub.2).sub.3N(CH.sub.3).sub.2      30     ##STR71##      ##STR72##      31     ##STR73##      ##STR74##      32     ##STR75##      ##STR76##      33     ##STR77##       NH.sub.2(CH.sub.2).sub.3N(CH.sub.3).sub.2      34     ##STR78##      NH.sub.2(CH.sub.2).sub.3N(C.sub.2 H.sub.5).sub.2      35     ##STR79##      ##STR80##      36     ##STR81##      NH.sub.2(CH.sub.2).sub.2N(CH.sub.3).sub.2      37     ##STR82##      NH.sub.2(CH.sub.2).sub.3N(CH.sub.2CH.sub.2 OH).sub.2      38     ##STR83##      ##STR84##      39     ##STR85##      ##STR86##      40     ##STR87##      ##STR88##      41     ##STR89##      ##STR90##      42     ##STR91##      NH.sub.2(CH.sub.2).sub.3N(CH.sub.3).sub.2      43     ##STR92##      NH.sub.2(CH.sub.2).sub.3N(C.sub.2      H.sub.5).sub.2

EXAMPLE 44

15.8 g of the dyestuff base of the formula ##STR93## are dissolved in1,400 ml of water by bringing the medium to pH 7. 1.6 g of an emulsifierprepared from lauryl alcohol and ethylene oxide are added, followed at20° by 16.4 g of cyanuric chloride in the course of 15 minutes while pH5.0-5.5 is maintained with 2N sodium carbonate solution. Thecondensation is complete after about 4 hours, a fine suspension havingformed. 40 g of 2-aminoethylpiperazine are added, and the mixture isheated initially at 75° to 80° for 2 hours and then at 90° to 95° for 4hours. It is allowed to cool down, and the partly precipitated dyestuffis salted out completely with sodium chloride, is filtered off withsuction, and is washed with sodium chloride solution.

The product is a dyestuff of the formula (I) in which R₁ and R₂ =Cl, R₃=H, m=0, n=1 and R₅ and R₆ = ##STR94##

λ_(max) =617 nm in 5% strength acetic acid.

Paper dyed blue can be obtained with this dyestuff by adding a solutionof the product obtained in 10% strength acetic acid to a suspension ofbleached pulp, stirring at 20° for 15 minutes, and using the colouredmaterial to produce sheets of paper on a sheet-former. The fact that thewaste waters are coloured only to a slight degree is indicative of highdegrees of exhaustion. The wet fastness properties of the dye papers areexcellent. C.I. indicator number 14.

EXAMPLE 45

10.0 g of the dyestuff base of the formula ##STR95## are dissolved at pH7-8 in 700 ml of water. The solution is added dropwise to a suspensionof cyanuric chloride prepared by dissolving 8.2 g of cyanuric chloridein 80 ml of acetone and pouring the resulting solution into 80 ml ofice-water. The reaction mixture is held at a temperature of 0° to 5°and, with 1N sodium carbonate solution, at pH 5.0-5.5. When the reactionhas ended after some hours, the precipitated condensation product isfiltered off with suction and is added to a mixture of 10.0 g of3-dimethylamino-1-propylamine and 200 ml of water. The mixture is thenheated initially at 45° to 50° for 2 hours and then at 75° to 80° for 5hours. The solution obtained is cooled down and either the dyestuff issalted out with sodium chloride, filtered off with suction and dried, orthe solution obtained is evaporated in vacuo in a rotary evaporator. Ineither case the product is a dark blue powder, namely a dyestuff of theformula (I) in which

R₁ and R₂ =Cl, R₃ =H, m=0, n=1 and

R₅ and R₆ =--N--CH₂ --CH₂ --CH₂ --N(CH₃)₂).

EXAMPLE 46

The condensation product of the formula ##STR96## obtained as in Example45 is isolated as described there and is added to a solution of 15.0 gof 2-hydroxyethylpiperazine in 200 ml of water. The mixture is heated at60° for 2 hours and then at 95° for 4 hours. When the mixture has cooleddown the resulting dyestuff is salted out with sodium chloride, isfiltered off with suction, is washed with dilute sodium chloridesolution, and is dried.

The product has the formula (I) in which

R₁ and R₂ =Cl, R₃ =H, m=0, n=1 and

R₅ and R₆ = ##STR97##

λ_(max) --578 nm and 629 mm in 5% strength acetic acid.

Paper is dyed from dilute acetic or formic acid solutions in the sameway as described in Example 44. C.I. indicator number 14.

Further dyestuffs which dye paper a reddish blue from solutions indiluted weak acids are obtained by condensing the triphendioxazinesgiven in column 2 of Table II with cyanuric chloride in a molar ratio of1:2 and condensing the resulting intermediates with 4 moles of the aminecomponent of column 3, the result being dyestuffs of the formula (I) inwhich m=0, n=1 and R₅ =R₆. C.I. indicator number 14.

                                      TABLE II                                    __________________________________________________________________________    Ex-                                                                           am-                                                                           ple                                                                           No.                                                                              Triphendioxazine component            Amine component                      __________________________________________________________________________    47                                                                                ##STR98##                            NH.sub.2(CH.sub.2).sub.3N(CH.sub.                                             3).sub.2                             48 "                                                                                                                    ##STR99##                           49                                                                                ##STR100##                           NH.sub.2(CH.sub.2).sub.3N(C.sub.2                                              H.sub.5).sub.2                      50 "                                     NH.sub.2(CH.sub.2).sub.3N(CH.sub.                                             2CH.sub.2 OH).sub.2                  51 "                                     NH.sub.2(CH.sub.2).sub.3N(CH.sub.                                             3).sub.2                             52                                                                                ##STR101##                                                                                                          ##STR102##                          53                                                                                ##STR103##                                                                                                          ##STR104##                          54 "                                                                                                                    ##STR105##                          55                                                                                ##STR106##                           NH.sub.2(CH.sub.2).sub.3N(CH.sub.                                             2CH.sub.2 OH).sub.2                  56                                                                               ##STR107##                                                                                                              ##STR108##                       57                                                                                ##STR109##                                                                                                          ##STR110##                          58 "                                     NH.sub.2 (CH.sub.2).sub.3N(C.sub.                                             2 H.sub.5).sub.2                     59 "                                     NH.sub.2(CH.sub.2).sub.2N(CH.sub.                                             3).sub.2                             60 "                                     NH.sub.2(CH.sub.2).sub.3N(CH.sub.                                             2CH.sub.2 OH).sub.2                  61 "                                                                                                                    ##STR111##                          62 "                                                                                                                    ##STR112##                          63 "                                                                                                                    ##STR113##                          64 "                                                                                                                    ##STR114##                          65 "                                     NH .sub.2(CH .sub.2CH .sub.2NH)                                               .sub.2CH .sub.2CH .sub.2NH.sub.2     66 "                                     NH.sub.2(CH.sub.2).sub.2NH(CH.sub                                             .2).sub.2NH.sub.2                    67 "                                     NH.sub.2CH.sub.2CH.sub.2N(C.sub.2                                              H.sub.5).sub.2                      68 "                                     NH.sub.2(CH.sub.2).sub.3NHCH.sub.                                             3                                    69 "                                                                                                                    ##STR115##                          70 "                                     NH.sub.2CH.sub.2CH.sub.2NHCH.sub.                                             2CH.sub.2 OH                         71 "                                     NH.sub.2(CH.sub.2).sub.6NH.sub.2     72 "                                                                                                                    ##STR116##                          73 "                                                                                                                    ##STR117##                          74                                                                                ##STR118##                           NH.sub.2(CH.sub.2).sub.3N(CH.sub.                                             3).sub.2                             75                                                                                ##STR119##                                                                                                          ##STR120##                          76                                                                                ##STR121##                           NH.sub.2(CH.sub.2).sub.3N(C.sub.2                                              H.sub.5).sub.2                      __________________________________________________________________________

EXAMPLE 77

12.0 g of a triphendioxazine of the formula ##STR122## are suspended in120 ml of dimethylformamide. 10.8 g of cyanuric chloride are addeddropwise at 25° in the course of 15 minutes, whereupon the colour of thesuspension gradually changes from blue to violet and then to reddishbrown. The suspension is stirred for a further 3 hours until thestarting dyestuff base has disappeared. A sample of the substance formedwill then produce a pure reddish violet solution in warm nitrobenzene.The precipitate formed is filtered off with suction and washed withmethanol. After drying in an air stream the condensation productobtained is added to 70 ml of 2-aminoethylpiperazine. The solution isinitially stirred at 35° for 3 hours and then at 70° for a further 5hours. After the condensation has ended the solution is diluted with 15%strength sodium chloride solution, and the precipitated dyestuff iswashed with sodium chloride solution and dried.

The product obtained has the formula (I); in which

R₁ and R₂ =Cl, R₃ =H, and m and n=0 and

R⁵ and R⁶ = ##STR123##

λ_(max) =554 nm in 5% strength acetic acid.

For dyeing paper, 10 g of the dyestuff obtained are dissolved in 30 mlof acetic acid and 60 ml of water. The ready-to-use solution can bediluted for dyeing as required. The bluish violet dyeings obtained onpaper with high degrees of exhaustion have excellent wet fastnessproperties. C.I. indicator number 12.

EXAMPLE 78

10.6 g of the dyestuff base of the formula ##STR124## aredissolved/suspended in 100 ml of N-methylpyrrolidone. 7.6 ml ofN,N-dimethylaniline are added, followed at 25° by the dropwise additionof 5.3 ml of cyanuric fluoride. After 1 hour the temperature is raisedto 45° and the mixture is stirred at said temperature for a furtherhour. It is cooled down, 300 ml of methanol are added dropwise, theprecipitate is filtered off with suction, and the filter cake is washedwith methanol. 16.0 g of the condensation product obtained are added to60 ml of 3-dimethylamino-1-aminopropane in the course of 1 hour duringwhich the temperature is not allowed to exceed 35°, the solution isstirred at 35° to 40° for 3 hours and then at 60° for a further 5 hours.After cooling down, the solution obtained is added dropwise to 800 ml of20% strength sodium chloride solution, and the precipitated product isfiltered off with suction, is washed with sodium chloride solution and,if desired, is dried.

The product is a dyestuff of the formula (I), in which

R₁ and R₂ =Cl, R₃ =H, m and n=0 and

R₅ and R₆ =--NH--CH₂ --CH₂ --N(CH₃)₂

λ_(max) =547 nm in 5% strength acetic acid.

For dyeing paper, the dyestuff is brought into the protonated form as inExample 77 and the protonated form is used to prepare a ready-to-usesolution. Very wet-fresh bluish violet dyeings are likewise obtained onsized and unsized paper. The fact that the waste waters are onlyslightly coloured is indicative of high degrees of exhaustion. C.I.indicator number 12.

EXAMPLE 79

12.0 g of 3,10-diamino-6,13-dichlorotriphendioxazine are reacted with10.8 ml of cyanuric fluoride in 120 ml of dimethylformamide in line withthe method described in Example 77, and the precipitated condensationproduct is isolated. This intermediate is added to 75 ml ofN-hydroxyethylpiperazine and the reaction mixture is initially heated at50° to 55° for 30 minutes during which it becomes very thick and then at80° C. for an additional 2 hours. The mixture is cooled down to 50°, and250 ml of acetone are then added dropwise. The resulting precipitate isfiltered off with suction at 20° and is washed with acetone.

The resulting dyestuff of the formula (I) in which R₁ and R₂ =Cl, R₃ =H,m and n=O and

R⁵ and R₆ = ##STR125##

λ_(max) =555 nm in 5% strength acetic acid

can likewise be used for the violet dyeing of paper as described at theend of Example 77. Its application properties are similar to those ofthe dyestuff described there. C.I. indicator number 12.

EXAMPLE 80

10.0 g of the triphendioxazine of the formula ##STR126## are suspendedin 100 ml of dimethylformamide. 9.0 ml of cyanuric fluoride are addeddropwise in the course of 10 minutes. The suspension is stirred at roomtemperature for 1 hour and then at 35° to 40° for 21/2 hours. When thesuspension has cooled down to 20° the brownish precipitate is filteredoff with suction, is washed with methanol and is sucked dry. 17.0 g ofthe product obtained are added to 100 ml of1-amino-3-dimethylaminopropane in the course of half an hour duringwhich a mild exothermic reaction occurs. The mixture is then heated to75° in the course of about 30 minutes, and said temperature ismaintained for 2 hours. The resulting solution is cooled down and pouredinto 2 liters of 25% strength sodium chloride solution. The resultingsuspension is filtered with suction, and the filter cake is washed withsodium chloride solution. The product obtained has the formula (I) inwhich

R₁ and R₂ =H, R₃ =H, m and n=0 and

R₅ and R₆ =--NH--(CH₂)₃ --N(CH₃)₂

λ_(max) =549 nm in 5% strength acetic acid.

For application to paper, the product obtained is dissolved in diluteacetic acid as described in Example 77. The dyestuff dyes paper insomewhat more reddish violet shades than the dyestuff of Example 78does. C.I. indicator number 12.

EXAMPLE 81

12.0 g of the triphendioxazine component of the formula ##STR127## arecondensed at 0° to 5° and pH 8.5 in water-acetone with 8.4 g of cyanuricchloride as described in Example 1. After the reaction has ended, thebatch is raised to 20° to 25°, and 2.5 g of 2-aminoethanol mixed with 25ml of water are then added dropwise in the course of 30 minutes duringwhich the pH may be allowed to rise to 9.0 and, after the dropwiseaddition of the aminoethanol, is maintained between 8.5 and 9.0 by meansof 1N sodium hydroxide solution. The condensation is complete afterabout 3 hours. All of the product is precipitated by adding 25% strengthsodium chloride solution, and the precipitate is filtered off withsuction and washed with 15% strength sodium chloride solution. Theintermediate product obtained has essentially the formula ##STR128##

The moist filter cake of the intermediate product is introduced into amixture of 10.0 g of 2-aminoethylpiperazine and 300 ml of water, and themixture is heated to 95° to 100° in the course of 30 minutes. 3 hourslater the solution is cooled down to room temperature. The productformed is salted out with sodium chloride, is filtered off with suction,and is washed with 20% strength chloride solution.

The dyestuff obtained has the formula (I) where

R₁ and R₂ =Cl, R₃ and R₄ =H, A=ethylene, m=1, n=1 and ##STR129## R₅ =

λ_(max) =634 nm in 5% strength acetic acid.

Dissolved in dilute acetic acid or formic acid the dyestuff dyes paperin bright blue shades. The dyeings have very good light and wet fastnessproperties. C.I. indicator number 14.

Further, similar blue dyestuffs are obtained by condensing thebis-dichlorotriazinyl compound first prepared in Example 81 initiallywith the R₆ --H amines of Table III in a molar ratio of 1:2 and thenwith the R₅ --H amines. C.I. indicator number 14.

                  TABLE III                                                       ______________________________________                                        Example No.                                                                             R.sub.6 --H  R.sub.5 --H@                                           ______________________________________                                        82        Diethanolamine                                                                             3-Dimethylamino-1-amino-                                                      propane                                                83        Diethylamine 2-Aminoethylpiperazine                                 84        Dimethylamine                                                                              2-Diethylamino-1-amino-                                                       ethane                                                 85        Morpholine   2-Aminoethylpiperazine                                 86        Diethanolamine                                                                             2-Aminoethylpiperazine                                 87        Ammonia      2-Aminoethylpiperazine                                 88        Methylamine  2-Aminoethylpiperazine                                 89        Piperidine   2-Aminoethylpiperazine                                 90        2-Aminoethanol                                                                             2-Aminoethylpiperazine                                 ______________________________________                                    

EXAMPLE 91

10.0 g of triphendioxazine of the formula ##STR130## 80 ml ofnitrobenzene and 12.0 g of cyanuric chloride are heated at 120° C. for 4hours. When the suspension has cooled down the precipitate is filteredoff with suction at 20° and is washed with methanol. 16.0 g of theintermediate product obtained are introduced into 60 ml of1-amino-3-dimethylaminopropane. The temperature is raised to 74° for 2hours, and the working up then takes the form described in Example 78,namely the reaction mixture is added to sodium chloride solution. Theproduct obtained has the formula (I) where

R₁ and R₂ =Cl, R₃ =H, m and n=0 and

R₅ and R₆ =--NH--(CH₂)₃ --N(CH₃)₂

and is identical to that of Example 78.

EXAMPLE 92

13.5 g of the dyestuff of the formula (VII) where

q=2 and R'₅ = ##STR131## which is obtained in Example 3 aredissolved/suspended at 20° in 150 ml of water. 5.0 ml of dimethylsulphate are added dropwise, and the reaction mixture is held at pH8.5-9.0 by means of 1N sodium hydroxide solution.

After 4 hours the suspension obtained is heated at 80° to 85° for 1 hourat the same pH, and is then cooled down to 20°, and the resultingproduct is isolated by filtering with suction.

The result is a dyestuff of the formula (VII) where

q=2 and R₅ = ##STR132##

λ_(max) =637 nm in 5% strength acetic acid

which can likewise be used for the wet-fast dyeing of paper from acidsolution. C.I. indicator number 14.

Alternatively, the suspension obtained on cooling down to 20° can alsobe turned into a solution by adding acetic acid or methanesulphonicacid, and the resulting solution can be directly used for dyeing paper.

EXAMPLE 93

9.0 g of the dyestuff obtained in Example 78 are suspended in 90 ml ofwater, 0.1 ml of an emulsifier based on lauryl alcohol and ethyleneoxide are added, and the suspension is brought to pH 10 by means of 1Nsodium hydroxide solution, whereupon it thickens. 6.0 g of dimethylsulphate are then added dropwise at 25° while pH 9.0-10.0 is continuedto be maintained. The batch becomes thinner and finally turns into asolution. The solution is then stirred under the given conditions for 2hours and is then heated at 80° to 85° for an additional hour.

When there is no longer any detectable sodium hydroxide consumption, thesolution is cooled down. It contains a dyestuff of the formula (I) inwhich

R₁ and R₂ =Cl, R₃ =H, m and n=0, and

R₅ and R₆ = ##STR133##

λ_(max) =546 nm in 5% strength acetic acid.

For practical use, the solution is rendered weakly acid and, if desired,can be concentrated in vacuo. The solution obtained can likewise be usedto dye paper bluish violet, exhaustion of the dyestuff onto the paperbeing virtually complete. C.I. indicator number 12.

The triphendioxazine components listed in column 2 of Table IV can alsobe condensed with 2 moles of cyanuric chloride analogously to Example 93and the resulting intermediate product can be reacted with 4 moles ofthe amine of column 3, the products again being basic dyestuffs whichare soluble in weak acids and which are suitable for dyeing paper in thehues given in column 4.

      Example No. Triphendioxazine component Amine Component C.I. indicator     number           94      ##STR134##      NH.sub.2(CH.sub.2).sub.3N(CH.sub.3).sub.2 13      95     ##STR135##      ##STR136##      13      96     ##STR137##      ##STR138##      13      97     ##STR139##      NH.sub.2(CH.sub.2).sub.3N(CH.sub.3 ).sub.2 13      98     ##STR140##      ##STR141##      13      99     ##STR142##      NH.sub.2(CH.sub.2).sub.3N(CH.sub.3).sub.2 12   100      ##STR143##      NH.sub.2(CH.sub.2).sub.3N(C.sub.2      H.sub.5).sub.2 13

EXAMPLE 101

12.0 g of the dyestuff of Example 7, which has the general formula(VII), are dissolved/suspended in 100 ml of water. 5.0 ml of dimethylsulphate are added dropwise while pH 8.5-9.0 is maintained by means of2N hydroxide solution. After 4 hours the temperature is raised to 50° C.and is maintained for 3 hours and is then raised to 75°-80° C. for anadditional hour. When sodium hydroxide solution is no longer consumed,the solution obtained is cooled down to room temperature and is broughtto pH 3.5 by means of 7 ml of glacial acetic acid.

The result is a ready-to-use paper-dyeing blue solution of the dyestuffof the formula (VII) where

q=2 and R'₅ = ##STR144##

λ_(max) =638 nm in 5% strength acetic acid. C.I. indicator number 14.

We claim:
 1. A triphendioxazine dyestuff of the formula ##STR145##wherein R'₁ and R'₂ each denote hydrogen or halogen,R'₃ and R'₄ eachdenote hydrogen or C₁ -C₄ -alkyl which can be substituted by OH orsulphato, A' denotes optionally branched C₂ -C₆ -alkylene which can beinterrupted by O or S or be substituted by OH or the radicals ##STR146##which can be substituted by C₁ -C₄ -alkyl, or ##STR147## representsoptionally C₁ -C₄ -alkyl-substitutable piperazine, R'₅ and R'₆ denote aradical of the formula ##STR148## R'₇ -R'₁₁ each denote hydrogen or C₁-C₄ -alkyl which is optionally substituted by hydroxyl, C₁ -C₄ -alkoxy,halogen, cyano, C₁ -C₄ -alkoxycarbonyl or C₁ -C₄ -alkylcarbonyl and R'₁₁also denotes optionally C₁ -C₄ -alkyl-, hydroxyl-, C₁ -C₄ -alkoxy- andhalogen-substituted benzyl or phenylethyl and B denotes C₂ -C₆-alkylene, cyclohexylene, phenylene or an optionally C₁ -C₄-alkyl-substituted radical of the formulae ##STR149## represents anoptionally C₁ -C₄ -alkyl-substituted piperazine or imidazlidine ring, orR'₈ --N--R'₉ signifies an optionally C₁ -C₄ -alkyl-substitutedpiperidine, morpholine, piperazine or pyrrolidine ring or ##STR150##signifies an optionally C₁ -C₄ -alkyl-substituted pyridinium radical,X.sup.(-) signifies an anion, m denotes 0 or 1 and n denotes 0 or
 1. 2.A triphendioxazine dyestuff according to claim 1, wherein R'₁ and R'₂each represent chlorine, R'₃ and R'₄ each represent hydrogen or C₁ -C₄-alkyl.
 3. A triphendioxazine dyestuff according to claim 1 of theformula ##STR151## wherein q represents 2, 3 or
 4. 4. A riphendioxazinedyestuff according to claim 3 whereR'₅ represents ##STR152## and theammonium compounds of these amines obtained by quaternisation with R"₁₁-X, with R"₁₁ and R'₁₂ each represent hydrogen, methyl or ethyl, R₁₃represents OH or N(R'₁₂)₂ and X represents a radical X.sup.(-) which isdetachable in the form of the anion X.sup.(-).